Dialkoxy phenylene bis-sulfonamides

ABSTRACT

DIALKOXY PHENYLENE BIS-SULFONAMIDES HAVING UTILITY AS FOLIAGE FUNGICIDES.

United States Patent Oflice 3,769,342 Patented Oct. 30, 1973 U.S. Cl.260556 S 4 Claims ABSTRACT OF THE DISCLOSURE Dialkoxy phenylenebis-sulfonamides having utility as foliage fungicides.

This application is a divisional of Ser. No. 804,998, filed Mar. 6,1969, now Pat. No. 3,621.032.

Polysulfur tricyclic compounds, wherein two substituted aromatic ringsare attached to each other through two tetrasulfide links, can be split.

PRIOR ART Although applicants are not aware of any prior art that isrelevant to the invention, a brief discussion of the background inchemistry underlying the present invention may facilitate itsappreciation.

It has previously been reported [2. S. Ariyan and L. A. Wiles, J. Chem.Soc. 4709-12 (1962)] that the dimethoxybenzenes vary greatly in theirreactivity towards sulfur monochloride (Cl--SfiS-Cl). The order ofreactivity with (S C1 is para-dimethoxybenzene ortho-dimethoxybenzenemeta-dimethoxybenzene. The meta-disubstituted derivative is the mostreactive while the least reactive is the para-derivative. No catalystswere used in the reported reactions and the products were linearsulfides. Their reactions could be represented by the followingequations:

solvent (MeO) -RH ClS-S-C1 (MeOh-R-S-S-R-(OMe) I HI CHB- SCM 81 S C 3(III) SUMMARY OF INVENTION The invention relates to novel tricyclicsystems in which two aromatic rings are attached to each other by twotetrasulfide links. The novel tricyclic systems may be represented bythe Formula (I) x s-s-s-s X wherein X is alkoxy (OR), alkylthio (SR) orhalogen, R being represented by straight or branched alkyl, hereinafterreferred to as cyclic-bis-tetrasulfides or CBT.

The invention is also concerned with a novel process for preparing thenovel cyclic-bis-tetrasulfides.

Considered from another aspect, the invention relates to novel compoundsobtained by the splitting of CBT.

As will be noted from Formula I of the novel cyclic-bistetrasulfides,the positions of substitution by the sulfur atoms onto the aromaticrings may vary and are in fact determined by the respective substituentson the ring.

The aromatic rings themselves are disubstituted with at least one alkoxygroup, a thioalykyl group or a halogen. The ring substituents arepreferably situated in parapositions respective to the ring. In FormulaI, X represents either an alkoxy group O-R; an alkylthio group S-R or ahalogen. Chlorine is a suitable halogen for the inventive purposes. Raymay be any alkyl group, either straight or branched. Preferred alkylsare the lower alkyls of from 1-5 carbon atoms.

The size of the central sulfur ring is determined by the position ofsubstitution of the sulfur atoms which may occur at 2:3-; 2:5-; or 226-depending on the nature of the ring substituents and particularly of X.

The cyclic-bis-tetrasulfides are high melting, yellow to deep orangecrystalline products which may be readily prepared by the reaction of apara-substituted alkoxybenzene with sulfur monochloride (ClSS-Cl) in thepresence of a catalyst. The reaction is advantageously carried out atelevated temperatures within the temperature range of about 4070 C. Aconvenient catalyst for the reaction is a Lewis acid type catalyst, suchas anhydrous aluminum chloride, boron trifluoride, tin or antimonychlorides and, preferably, a montmorillonite catalyst of the K-serieswhich is readily available from Chemical Products Division of ChemetronCorporation and designated hereafter Girdler Catalyst KSF/O. It has beenfound that the presence of a catalyst is of utmost importance for thepreparation of the cyclic-bis-tetrasulfides. A diluent should also bepresent. Suitable diluents are carbon disulfide, chloroform, carbontetrachloride, methylene dichloride, ethylene dichloride or, in general,halogenated aliphatic hydrocarbon solvents. Reaction at the boilingtemperature of the solvent or diluent is preferred. Most of theindicated solvents boil within the indicated preferred 40-70 C. range.

In the preparation of the cyclic-bis-tetrasulfides, the para-substitutedalkoxybenzene is vigorously stirred in the solvent with by weight of thecatalyst, to which is added sulfur monochloride (ClSSCl) in the samesolvent. After complete addition of the sulfur reagent and if noreaction is apparent, heat, for example, in the form of steam isapplied. Invariably hydrogen chloride gas begins evolving after all thesulfur monochloride has been added and the reaction mixture assumes adeep green color, due to the formation of a complex intermediate. Thereaction mixture is thus stirred and heated until all Table I lists anumber of cyclic-bis-tetrasulfides which have been prepared and theelemental analytical results obtained.

Step (2) Step three is a step similar to step two, whereby another moleof chlorine is lost intramolecularly (within the same molecule) by amechanism which favors such as cyclization to yield the inventivecyclic-bis-tetrasulfide of Formula I.

Step (3) TAB LE I.R AND X IN FORMULA (I) Calculated Found R X M.P.General formula C H S 01 C H S 01 CH3 OCHs 210-216 CmHmiOSa 36.34 3.0648.61 36.67 3.22 48.36 C2H5 0C2H5 185 02011240483 41. 07 4. 13 43. 8641. 34 4. O7 44. 24 CH3 0C2H5 158-60 01311200488 38. 82 3.62 46. 07 38.86 3.66 46.11 CH: 01 196-8 01111160201285 31.27 1.88 47.68 13.18 31. 621.91 47.63 13.06 Phom OCHz'Ph 172-5 04011310186 67.66 3 87 30. 79 67.903.98 30.63

the hydrogen chloride gas has evolved. The deep green The inventivecyclic-bis-tetrasulfides exhibit significant color has also disappearedat that time. The reaction time accelerator activity in rubbervulcanizing processes. This may vary from two to five hours. Thereaction mixture activity is particularly pronounced in thevulcanization of is then filtered While hot to cause separation from thestyrene butadiene rubber (SBR) and ethylene propylene catalyst and anorange solution results. Some of the soldiene rubber (EPDM as indicatedby Monsanto Rhevent may have to be evaporated off to allowcrystallizaometer tests. Comparison tests carried out with cyclic tionof the product. As will be seen from the examplesBi(2,5-bis-dithio-1,4-diethoxybenzene) and the prior art givenhereinbelow, in some cases work-up methods are commercial acceleratortetramethylthiuram disulfide, required whereas in others the productsare relatively inwhich is also known under the trademark Tuex,indisoluble and precipitate from the solution. For example, cated thatthe former compound is superior to Tuex in on standing of a reactionproduct solution obtained foam the vulcanizing of SBR.p-diethoxybenzene, large orange crystals appear, while The inventive CBTcompounds may be degraded or an extremely insoluble orange product isobtained from pli into useful new compounds. Depending on thep-dimethoxybenzene. Both these products are cyclic-bissplitting processto which the CBT compounds are subtetrasulfides. In the case ofinsoluble products soxhlet exj the following three groups of mp s maytraction method may have to be used to remove the prodthus be Obtained:not from the catalyst, since filtration of the hot reaction productsolution does not yield the desired separation. In respect to otherderivative, column chromatography on alumina is invariably of value,since any elemental sulfur is then removed on the alumina.

The orange crystals consist of the novel CBT com- R R R pounds. Theirstructure has been supported by a variety 4 (L of physical methods. Suchmethods as X-ray, Nuclear I I Magnetic Resonance (N.M.R.), Ultraviolet(U.V.), Infrared (I.R.), molecular weight and elemental analysis SH SCISO2C1 have been used to elucidate and conclude on the crystal- HS 015also line nature of these compounds.

A general scheme for the reaction steps may be represented by thefollowing: X X X Although applicants do not want to be limited by any(A) (B) (C) theories advanced by them, it is believed that the firststep in the reaction is a bis-chlorodithio-derivative formation(ClSSZS-S--Cl) where Z represents a divalent radical such as apara-substituted alkoxybenzene. Such intermediates from sulfurmonochloride reactions are known and have been reported in J. Chem. Soc.1725 (1962) wherein X and R have the above meaning.

(Step (1) Compounds of group A are para-substituted alkoxy- Lewis acidcatalyst benzenes with two mercapto groups and thus constitute HZH2C1SSC1 aromatic dithiols which are obtained by the hydrogenajgfg Z s S1+ Z tion of CBT under controlled conditions. By contrast, chlorinationunder anhydrous conditions in a non-polar Step two involves theformation of an intermediate with solvent, such as carbon tetrachloride,degrades CBT to re- 1083 of chlorine. Evidence for such reactions isavailable active compounds of group B, such as disulfenyl chloin theliterature. rides. Compounds of group B are difiicult to isolate and arethus used in situ. Chlorination of CBT in the presence of trace mountsof water in turn yields disulfonyl chlorides of group C.

Compounds A, B and C are bifunctional. They constitute new compositionsof matter, have utility per se,

Reduction products of CBT compounds The controlled hydrogenation of CBTresults in re duction to aromatic dithiols of group A. Such a processmay advantageously be carried out with a platinum sulfide catalystsupported on carbon. The hydrogenation is and may be sucfiessfuuy used ma variety of syntheses performed in a solvent, such as benzene ortoluene for for the pfesentanqn other useful compounds an average periodof four (4) hourn at a temperature gg g z gg gg fg g the compounds B andc of about 200 C. and at a pressure range of 900-1300 g1 p.s.i.g. SeeTable II.

TABLE II HS SH Calculated Found R X M. Position General formula C H S 01C 01H. 002m 117 2=5 CroHuOzSa 52.17 6.09 52.19 CH: 1 43.5-44 2:6-0111108201 40.66 3.41 40.95 CH3 OC2H4 69 2:5- CoHlzozsz 49.97 5.58 50-74C4H9 OCiHB 77-78 2:5 (31411220252 58. 70 7. 74 57.84 CH: OCHs 122 2:502111100232 47.49 4.98 47.93

The scheme for obtaining the compounds A, B and C A few examples arehere given of the feasibility of may be demonstrated by the following:this reaction in obtaining a series of aromatic dithiols. The nature ofR has previously been defined as a branched or unbranched aliphaticchain of carbon atoms, preferably C -C and X may be an alkoxy (OR) andS-S-S-S alkylthio (S-SR) where R may be similar to R; X may l also be ahalogen. The group A compounds may be fur- I I g 3. ther reacted toprepare a variety of bis-sulfides, disulfides, and polysulfides as shownin Table HI.

Reactions of compounds of group A with: (A) (B) (C) (1) Aliphatic oraromatic compounds containing a wherein Z represents thePara-Substituted y' reactive halogen will yield bis-monosulfides.benzene rings of Formula I.

In order to appreciate this aspect of the invention, it should beconsidered that there is nodirect convenient H base H way of preparingdimercapto-(p-substituted alkoxyben- 2R X+ HS-PSH R S (Z) S R ZHX zenes)or (alkoxy, alkylthio)-'benzenes. This invention, for the first time,proposes such derivatives Z(SH) where Z is the p-substitutedalkoxybenzene, X a halogen, designated (A), their chlorination productsZ(SC1)2 and R either an aliphatic branched or unbranched hydesignated(B), which are normally used in 'situ, and their drocarbon orsubstituted or unsubstituted aromatic ring. oxidation products Z(SO Cl)designated ((2). Methyl, ethyl, butyl, tert-butyl, phenyl, nitrophenyl,2-

It is well known that in sulfur monochloride reactions,chloro-4-nitrophenyl, polychlorophenyl compounds may polymers oftenoccur due to lengthening of the chains by thus be prepared. Table IIImerely lists a few possibilities sulfur atoms. In the formation of theinventive cyclic-bisin the series where x=1. tetrasulfides (CBT) whichare formed through interme- (2) With aliphatic or aromatic sulfenylhalides R' diates (CISSR-S--SC1), straight chain polymerization SCI,bis-disulfides are obtained. compounds are also obtained. As a matter offact and as has been stated hereinabove, after separation of the 2crystalline cyclic compounds, an orange colored oil is 0 obtained. Thisoil is a polysulfur linear polymer repm resented by the Formula V,wherein n=2 or 4 and Z is where, g Z 15 the as above and R 1sparwsubstituted alkoxybenzene. an aliphatic substituted or unsubstitutedsulfenyl halide, or an aromatic substltuted or unsubstituted sulfenylha- S lide. The ease of preparation of certain sulfenyl halides n ZrsnZjsh Z Sn makes the synthesis of such bis-disulfides readily avail-Therefore polymers of type V are formed, but their able. 11' may embracegroups such as the following degradation would also yield the compoundsof groups methyl-, ethyl-, propyl-, butyl-, chloromethyl-, chloro- A, Bnd C, ethyl-, trichloromethyl-, chlorobutyl-, phenyl-, chloro- It hasthus been found that the oily linear polymer phenyl-, polychlorophenyl-,methyphenyl-, trimethylproducts designated by V are also reduced to thesame phenyl, methyl-chlorophenyl-, nitrophenyl-, chloro-nitroaromaticdithiols as their corresponding cyclic crystalphenyl-, dinitro-pheny1-,methyl-nitrophenyl-, naphthyl-, line products (CBT). The reactionproducts obtained substituted naphthyl-, anthraquinoyland derivatives inthe preparation of CBT may thus be subjected directly and combinationsof any substituents for which the corto reduction without furtherseparation of the crystalline responding sulfenyl halide may readily beavailable. Table products and the orange colored oil.

III lists a few examples where x=2.

TABLE III P Calculated Analyzed 031- X R R x M.P tlon General formula CH S H Ethoxy- Ethyl.-. Methyl 1 109-11 2:5- CnHiaOzSz 55.78 7. 03 24.6.92 D (10..... Eth 1 78-785 215- CuHzzOzS: 58.69 7.74 22.38 7.84 17878.5 2:5- CmHztOzSa 61.11 8.33 20.38 8. 60 1 71-72 2:5- C1oH2sO2Sa61.11 8.33 20.38 8.33 1 78-79 2:5- ClsHaoOaSa 63.20 8. 84 18.72 9.04 11718 2:5- CrsHsuOzS: 63.20 8.84 18.72 8.56 1 56-57 2:5- C2oHa4O2S: 65.019.25 17.30 9.62 1 37-39 225- CzzHasOzS: 66.28 9.55 16.08 9.31 1 78-792:5- CHI-B40282 66.61 8.63 16.17 8.86 -do p-Nitrophenyl 1 205-6 2:5-CQZHZUOBSBNQ 13.57 Do-- --.do. TrichIOrOmethyL-.- 2 119-20 2:5-C1zHuOzS4Clc 24.18 40.11 Do do Benzo 1 1801 225- CuHnOaSg 65.72 5.0614.62 4.94 14. Do.. do.. o-Nitrophenyl 2 165 2:5- CzzHzoOsS4N9 49.223.76 23.90 4.03 4. Do -do PentachlorophenyL. 2 205 2:5- 02311110284011033.39 1.82 16.21 44. 81 1.81 Do do 2:4-dinitrophenyl--. 2 198-9 2:5-C22H1sOioS4N4 20.46 9.62 20.76 8.94 D ...do 2-nitllzro-4ichloro- 2 207-82:5- CzzHuOaSKJlzNz 21.25 11.75 4.64 20.50 11.43 5.11

p eny D0 .do 9-anthryl 3 165-6 215- CaaHiaOzSn 64. 46 3. 99 27.17 63.784.42 28.65

TABLE IV R I 0 I R-SOz- SO2-R' Calculated Analyzed R General formula C HS Cl N O H S 01 N Methyl 02111110582012 2. 41 70 47 19 Ethyl. CmHnOoSzCh3. 3 27 18 Methyl CsHrzOuSzNz Ethyl. CmHazOaSzNz Do Cyclohexylamlno255-256 C22HaaOoSzNt No'rE.-Certain bis-sultonamides have been listed inTable IV.

(3) With chlorodithio derivatives (R SSCl) or derivatives (R S Cl) wheren=2 or greater.

Table III lists an example of this reaction.

The above thus relates to the compounds of Group A as Products of typeR"'SS(Z)--SSR' may also be obtained by the anhydrous chlorination of CBTin carbon tetrachloride or chloroform at a temperature of 5 to 0 C.yielding disulfenyl chlorides Cl-S-ZS C1 (B). The Group B compounds,which were not isolated, react readily with desired mercaptans orthiophenols after removal of sulphur chlorides (S Cl and SCl which areformed during the chlorination of the CBT. R'SH+CI-S(Z)-S-CI+HS R"'R'S-S (Z)-S--S-(Z)S-S-R+2HC1 These reactions are advantageously carriedout in inert solvents such as carbon tetrachloride or chloroform. Thechlorination of CBT products on the other hand in acetic acid and in thepresence of a trace amount of water gives good yields of thecorresponding bis-sulfonyl chlorides of Group C. This procedure ofpreparing sulfonyl chlorides is well known, however, the bis-sulfonylchlorides thus obtained are new compositions of matter and are usefulcompounds in a variety of reactions particularly in the preparation ofbis-sufonamides (see Table IV). It will be appreciated by those skilledin the art that a very large wherein X is alkoxy or chlorine; R is loweralkyl and Y is SH, SCI; SO Cl; alkyl-monothio, alkyl-monothio,

alkyl-dithio, trichloroalkyldithio, arylmonothio, aryldithio, aryltrithio, sulfonamido, alkyl sulfonamido, cycloalkyl-sulfonamido oraroyl-thio. Specific examples embraced by the general formula areAromatic dithiols 1 :4-dimethoxyphenylene-2 S-dithiol 1:4-diethoxyphenylene-2 5-dithiol 1 :4-dibutoxyphenylene-2 S-dithiol4-ethoxyl-methoxyphenylene-Z 5 -dithiol4-chloro-l-methoxyphenylene-2:6-dithiol Aromatic disulfonyl chlorides 1:4-dimethoxyphenylene-2:S-disulfonyl chloride 1 :4-diethoxyphenylene-25-disulfonyl chloride Derivatives of aromatic dithiols Monothioderivatives:

1 :4-diethoxyphenylene-2 5 bis- (thiomethane) 1 :4-diethoxyphenylene-2S-bis-(thioethane) 1 :4-diethoxyphenylene-2 5-bis- (thi-1-propane) 1:4-diethoxyphenylene-2 -bis- (thio-2-propane) 1 :4-diethoxyphenylene-25- bis-(thio-l-butane) l :4-diethoxyphenylene-2 5-bis- (thiO-Z-butane) 1:4-diethoxyphenylene-2 S-bis-(thiol-pentane) 1 :4-diethoxyphenylene-25-bis-(thio-1-hexane) 1 :4-diethoxyphenylene-2 S-bis (thiocyclohexane) 1:4-diethoxyphenylene-2 5 -bisthiobenzoyl) 1 :4-diethoxyphenylene-25-bis- (thio-p-nitrobenzene) Dithio derivatives:

1 :4-diethoxyphenylene-2 5-bis- (dithiochloromethane) 1:4-diethoxyphenylene-2 S-bis- (dithio-o-nitrobenzene 1:4-diethoxyphenylene-2 5-bis-(dithio-2-nitr0-4- chlorobenzene) 1:4-diethoxyphenylene-2 S-bis-(dithio-pentachlorobenzene) Trithioderivatives:

1 :4-diethoxyphenylene-2 5-bis- (trithio-9-anthracene) Derivatives ofaromatic disulfonyl chloride 1 4-dimethoxyphenylene-2 5-bis-sulfonamide1 :4-diethoxyphenylene-2 5-bis- (n-butylsulfonamide) 1:4-diethoxyphenylene-2 5 bis- (dicyclohexylsulfonamide) The inventionwill now be described by several examples, it being understood, however,that these examples are given by way of illustration and not by way oflimitation and that many changes may be effected without affecting inany way the scope and spirit of the invention as recited in the appendedclaims.

In each of Examples 1-5, the catalyst used was the Girdler CatalystKSF/O previously referred to.

EXAMPLE 1 Preparation of cyclic bi(2,5-bis-dithio-1,4-dimethoxybenzene)R=CH X=OCH in (I) 1,4-dimethoxybenzene (966 g., 7.0 moles), methylenedichloride (1500 cc.), sulfur monochloride (938 g., 7.0 moles) andcatalyst (70 g.), were mixed and heated on a steam bath. A greencoloration developed and HCl evolved copiously; I -ICl liberationgradually subsided by the end of six hours. The reaction mixture wasthen filtered hot through a Buchner funneel, thereby removing anyunreacted starting materials which are soluble in the solvent The orangecrystalline filtrate which was contaminated with catalyst weighed 1035g. This material is extremely insolfi ble and was removed from thecatalyst by Soxhlet extraction with toluene to give 52.2% yield of anorange solid which melts with vitrifaction 210-212. The material may berecrystallized from monochlorobenzene or from toluene as orange platesM.Pt. 212-214 C.

10 EXAMPLE 2 Preparation of cyclic bi(2,5-bis-dithio-1,4-diethoxybenzene'R=C H X==OC H in (I) 1,4-diethoxybenzene (332 g., 2.0 moles) methylenedichloride (500 cc.), sulfur monochloride (268 g., 2.0 moles) andcatalyst (20 g.), were mechanically stirred for 16 hours. Severalminutes after mixing of the reactants, a slight exotherm reaction isnoted, accompanied by copious evolution of hydrogen chloride gas. At theend of 16 hours the reaction mixture was warmed to 40 C. for one hour,then cooled down to room temperature. Filtration yielded 234 g. oforange crystal-line solid mixed with catalyst. Extraction withchloroform yielded 144 g. of product (59.5% yield), M.Pt. 185-7" withvitrifaction after several recrystallizations from chloroform.

EXAMPLE 3 Preparation of cyclic bi(2,5-bis-dithio-4-ethoxyanisole R=CHX=-OC H in (I) 4-ethoxyanisole (76 g., 0.5 mole), chloroform ml.),sulfur monochloride (67 g., 0.5 mole), and catalyst (5 g.) were mixedand mechanically stirred at room temperature for 4 hours, dduring whichtime hydrogen chloride evolved copiously. The mixture was then heated ona steam bath for an hour and filtered hot to remove the catalyst. Thecondensed and cooled filtrate was then chromatographed on an aluminacolumn using chloroform as eluent. The bright yellow main fraction wassolvent stripped. The orange plastic residue possessed a strong odor of4-eth0xyanisole. A single wash with diethyl ether caused precipitationof fine orange crystals which melted at 158-60 C. with vitrifaction.Recrystallization from cyclohexane several times gave large orangecrystals in 60% yield, M.Pt. 156-8 with vitrifaction.

EXAMPLE 4 Preparation of cyclic bi(2,6-bis-dithio-4-chloroanisole) ==CHX=Cl 4-chloroanisole 142 g., 1.0 mole), carbon tetrachloride (250 cc.),sulfur monochloride (134 g., 1.0 mole) and catalyst (15 g.), were mixedand refluxed on a steam bath until no more hydrogen chloride evolved.The reaction mixture was then filtered hot to remove the catalyst. The

resulting filtrate was vacuum-stripped of solvent to leave a dark,gold-colored oil, which was chromatographed on alumina using benzene aseluent. The bright yellow main fraction was partially solvent-strippedand left to stand overnight. The yellow precipitate which formed wascollected, recrystallized twice from benzene, and yielded bright yellowneedles, M.Pt. 182 C.

EXAMPLE 5 Preparation of cyclic=bi-(2,5-bis-dithio-1,4-dibenzyloxybenzene) R=Ph-CH X'= O-CH -Ph in (I)1,4-dibenzyloxybenzene (58 g., 0.2 mole), methylene dichloride (200ml.), sulfur monochloride (27 g., 0.2 mole) and catalyst (2 g.) weremixed and refluxed for 4 hours. The reaction mixture was filtered hot toremove the catalyst. The resulting filtrate was vacuum-stripped ofsolvent. The yellow orange residue was twice chromatographed on aluminawith chloroform as eluent in the first instance and benzene as eluent onthe second column. The yellow residue was recrystallized several timesfrom benzene to yield 3 g. (4% yield) of tiny yellow crystals M.Pt.172-5 C., with vitrifaction.

EXPERIMENTAL SECTION IN RESPECT TO DEGRADATION OF CBT Tables II, III andIV list the new compositions of matter which have been prepared fromCBT. The new compounds have been fully characterized analytically. Beloware listed some general and specific examples.

GENERAL REACTIONS Reduction of CBT to aromatic dithiols of Group AExamples are listed below of some reduction runs of some CBT compoundsusing benzene as the solvent medium (Table II).

Chlorination of CBT in anhydrous media to disulfenyl chlorides of GroupB CBT (10 g.) in chloroform (50 cc.) was cooled to 50 C. in an ice/waterbath. Chlorine was bubbled until the orange solution assumed a rubyredcoloration. This procedure lasted about 30 minutes. The solvent andsulfur chlorides S Cl and SCl which were formed were removed undervacuum distillation at around 30 C. when a red oil was obtained. Thiswas the disulfenyl chloride of Group B. These products could be usedwithout further purification as intermediates in preparing bis-sulfidesR'S-SZ-SSR' by reacting the disulfenyl chlorides with appropriatemercaptan or thiophenols in either chloroform or carbon tetrachloride.Table III lists such possible products where x=2.

Chlorination of CBT in acetic acid with a trace of water present toyield disulfonyl chlorides of Group C Through CBT g.) in glacial aceticacid (250 cc.) and water (20 cc.), chlorine gas was bubbled at a slowrate without allowing the temperature to rise above 45 C. Chlorinationwas carried out for about 90 minutes. The orange crystalline CBTgradually disappeared and a pale yellow white disulfenyl chlorideappeared instead. The product was filtered and may readily be used as anintermediate in a variety of possible reactions as discussed herein.Table IV lists some of the derivatives prepared and analyticallycharacterized.

EXAMPLE 6 Method of preparing bis-alkylthio derivatives Dialkyl sulfate(1 mole) or alkyl halide (2 moles) is added to the aromatic dithiol (1mole) in 20% sodium hydroxide solution (0.4 kg. solution per mole). Thereaction mixture was refluxed for one hour. The mixture was then cooledin an ice bath. Crude alkyl sulfide was then collected by filtration andrecrystallized from ethanol R-SZ-SR where Z is a disubstituted phenyleneradical such as 1:4 diethoxyphenylene-radical and R is lower alkyl,straight chain, branched chain or cyclic structure comprising from 1-6carbon atoms.

SPECIFIC REACTIONS Analytical data for all the compounds are listed inTables II, III and IV.

EXAMPLE 7 Preparation of 1 :4-diethoxyphenylene-2 S-bis- (thiomethane)Dimethyl sulfate (12.6 g., 0.1 mole) was added to 1:4 diethoxyphenylene2:5-dithiol (11.5 g., 0.05 mole) in 20 g. sodium hydroxide solution (4g. NaOH, 0.1 mole) and the mixture was refluxed one hour. After coolingin an ice bath for one-half hour, the crude solids were filtered andwashed several times with water. Recrystallization from ethanol gave 9g. (70% yield) of yellow crystals, M.Pt. l091l1 C.

(iKhHs S-CHa CHsS EXAMPLE 8 Preparation of 1:4-diethoxyphenylene2:5-bis- (thiobenzoyl) EXAMPLE 9 Preparation of 1 :4-diethoxyphenylene-2S-bis- (thio-p-nitrobenzene) 1:4-diethoxyphenylene 2:5-dithiol (2.3 g.)in ethanol (100 cc.) were added to 3.2 g. of p-chloronitrobenzene inethanol (50 cc.) and water (20 cc.). The mixture was heated until allsolids dissolved. 10 cc. of 6 N solution of sodium hydroxide was thenadded. The resulting deep red solution was refluxed. Precipitationappeared after about 10 minutes but the mixture was refluxed for about ahalf hour. The reaction mixture was then allowed to cool and the yellowbis-monosulfide was filtered. Crude M.Pt. 199- 200. Recrystallizationfrom benzene and cyclohexane gave yellow needles, M.Pt. 205206.

EXAMPLE 10 Preparation of lz4-diethoxyphenylene2:5-bis-(dithiotrichloromethane) 1:4 diethoxyphenylene-2:S-dithiol (7.2g.) in glacial acetic acid (50 cc.) was added to 14.4 g. oftrichloromethanesulfenyl chloride in acetic acid (50 cc.). The mixturewas refluxed, copious fumes of HCl evolved, and the solution turnedorange. The refluxing was continued until no more hydrogen chlorideevolved. The solution was cooled on ice and Ya yellow precipitateappeared. This crude product (5 g., M.Pt. 111) was washed with ethylalcohol and finally recrystallized from ethanol, M.Pt. 118-120.

CCla-S-S EXAMPLE 11 Preparation of 1:4-diethoxyphenylene2:5-bis-(dithiopentachlorobenzene) To 1:4-diethoxyphenylene 2:5-dithiol(5.6 g.) in carbon tetrachloride (50 cc.) was added slowly with stirringpentachlorobenzenesulfenyl chloride (12.8 g.) in carbon tetrachloride(150 cc.).. Hydrogen chloride began evolving and the mixture wasrefluxed until no more hydrogen chloride gas evolved. On evaporating thesolvent, substantially quantitative yield of the product is obtained.Crude M.Pt. 201-4. Recrystallization from carbon tetrachloride andpetroleum ether gave M.Pt. 205.

m, c1 c1 c1 c1 s-s -01 c1 -s-s 1' in EXAMPLE 12 Preparation of1:4-diethoxyphenylene-2:S-bis- (trithio-anthracene) EXAMPLE 13Preparation of 1:4-diethoxyphenylene-2:5-disulfonyl chloride Group C,R=C -H =0C H CBT was supplied in the form of bis-(p-diethoxyphenylenetetrasulfide) (4 g.) in acetic acid (100 cc.) cc. of water were addedand chlorine gas was bubbled through the mixture. The temperature wasnot allowed to rise above 45 C. Chlorination was continued for 75minutes when straw colored crystals appeared. Crude yield was 3.5 g. ofdisulfonyl chloride, M.Pt. 189-190. Recrystallization from cyclohexanegave pale yellow crystals, M.Pt. 190-191.

. CaHs S OgCl hHs EXAMPLE 14 Preparation of 1:4-diethoxyphenylene bis-(2 5 -di-cyclohexylsulfonamide) 1:4diethoxyphenylene-Z:5-disulfonychloride (3.6 g, 0.01 mole) in benzenecc.) was gradually added to cyclohexylamine (3.6 g, 0.04 mole) withshaking at room temperature. The reaction was slightly exothermic. Thereaction product was then refluxed for 30 minutes and left overnight.The product was then well washed with water, separated, and the benzeneremoved. The white bis-sulfonamide obtained was crystalline and has acrude M.Pt. of 255, yield 4 g. It may be rec'rystallizedfrom dioxane toa constant M.Pt. 255-256.

EXAMPLE 15 Preparation of the bis-sulfenyl chloride by chlorination ofthe CBT product or the diothol The example discussed hereinabove refersto the chlorination of the dithiol. The use of the dithiol avoids anyby-products such as sulfur chlorides being formed. Thus1:4-diethovyphenylene-2:S-diothiol (4.6 g.) in carbon tetrachloride (25cc.) was'cooled in ice to 0. To this solution was added an ice coldsolution of chlorine (2.8 g.) in carbon tetrachloride (100 cc.),gradually with constant shaking. Hydrogen chloride gas evolved and thesolution assumed a red color. The solvent was then removed under vacuumon a steam bath and ared fuming oil was obtained which is the disulfenylchloride. This may be used as an intermediate by reacting it with twovmoles of a mercaptan or thiol in an inert solvent. Thus addingpentachlorothiophenol in methylene dichloride with stirring to the aboveprepared disulfenyl chloride followed by gentle warming and subsequentlyrefluxing until all evolution of hydrogen chloride gas ceased, resultedin the preparation of 1:4- diethoxyphenylene-Z 5-bis(dithiopentachlorobenzene) M.Pt. 204. This product was identical to thatobtained a EXAMPLE 16 Herbicidal activity Weeds reduce crop yields andinterfere with harvesting a quality crop. Herbicides have been shown'tobe useful tools to control undesirable foliage on agricultural land. TheGroup A and B compounds of the present invention may be successfullyused as herbicides to control young weed seedlings. The chemicals arespecifically useful in controlling undesirable foliage. The followingmethods were employed to test the herbicidal activity.

A spray solution containing 2000 parts per million of chemical to waterwas made by first dissolving two tenths of a gram of chemical in 5milliliters of acetone and 30 milligrams of isooctyl phenyl polyethoxyethanol. This preparation was then dispersed in 85 ml. of water makingan aqueous spray solution. A potted mixture of four pregrown seedlingdicotyledon weeds (broad leaf) and three seedling monocotyledon weeds(grass) were sprayed with the prepared solution to the point ofrun-oflt. The plants were held in the greenhouse for one week. Percentweed control ratings were taken on the basis of the untreated plants.The following Table V illustrates the result:

TABLE v Percent weed control Applieation rate Broad Dithicls (p.p.m.)leaf Grass 2, 000 90 so 000 97 o 2, 000 100 75 Compound No. 1 had thefollowing composition:

IHfi Compound No. 2 had the following composition:

11s SH Compound No. 3 had the following composition:

( JzHs EXAMPLE 17 Fungicidal activity The control of foliage diseases onplants is essential in order to prevent crop failure from epidemicdiseases, and to maintain good yield and quality of agricultural produceso that requirements for marketing and consumption can be met.

Group C compounds were evaluated as foliage fungicides by their abilityto protect plants from subsequent infection by fungus diseases.

One gram of the chemical to be tested was ground with three ml. ofacetone and 50 mg. of a non-ionic surfaceactive agent (a Triton X-100condensation product of an alkyl phenol and ethylene oxide). The acetoneand surface-active agent are known to be inactive in the biologicaltests run. The mixture was diluted with water, giving suspensionscontaining 500 and 2000 ppm. of the chemical. These suspensions weresprayed on duplicate six inch tomato plants (variety Clarks EarlySpecial) using a gun- 16 type sprayer which delivered 2.5 ml. persecond. The plants were then placed in the greenhouse, together withuntreated check plants. Twenty-four hours later the treated anduntreated check plants were inoculated with a suspension of Alternariasolani spores by means of a 20 second spray from an atomizer sprayer(delivery rate one ml. per second). The plants were then kept overnightin a controlled chamber at a temperature of 75 F. and relative humidity.In the morning the plants were transferred to the greenhouse. Three dayslater the disease was scored by comparing the number of disease lesionsof the treated plants with the untreated check.

The formula to determine percent control is:

Avg. no. lesions on treated plant 100 (Avg. no. lesions on untreatedplant percent control The results are listed in the following Table VI.

From the above table it may be seen that these compounds, as an example,have pronounced fungicidal activity in controlling Alternaria EarlyBlight disease of tomatoes by foliar application of the chemicals.

Disulfenyl chlorides of group B The compounds of group B (disulfenylchlorides) are normally used in situ and will yield, on reacting withthiols, compounds similar to types which also are obtained by reactingthe dithiols of group A mentioned pre- Therefore the derivativesmentioned above are applicable.

What is claimed is:

1. A compound of the formula wherein X is selected from the groupconsisting of methoxy, ethoxy and benzyloxy;

R is lower alkyl of from 1 to 5 carbon atoms; and

Y is selected from the group consisting of sulfonamido, alkylsulfonamidoof from 1 to 4 carbon atoms and cyclohexylsulfonamido.

2. A compound of claim 1 in which X is ethoxy, R is ethyl and Y iscyclohexylsulfonamido.

17 18 3. A compound of claim 1 in which X is methoxy, R is 3,417,12212/1968 McManus 260-453 methyl and Y is sulfonamido. 2,965,655 12/ 1960Novello 260397.7 4. A compound of claim 1 in which X is ethoxy, R is3,344,138 9/1967 McManus 260-243 ethyl and Y is n-butylsulfonamido.

OTHER REFERENCES References Cited Manecke 61131.2 Makromol. Chem. 116,26-35 (1968). UNITED STATES PATENTS 3,574,739 4/1971 Wei et a1. 260556HENRY ULES Pnmary Examme' 3,344,138 9/1967 McManus 260243 G. T. TODD,Assistant Examiner 3,356,692 12/1967 Hotstman at al. 260-3472 10

